Stable polymer composition with improved discoloration resistance

Abstract

The present invention relates to a stabilized polymer composition comprising an organic polymer material to be stabilized and a stabilizer composition comprising at least one UV absorber selected from the class of o-hydroxyphenyl-triazine UV absorbers; a secondary hindered amine light stabilizer (sec.-HALS); at least one antioxidant selected from the group consisting of hindered phenols, phosphites, phosphites, or any mixture thereof; a tertiary hindered amine light stabilizer (tert.-HALS); an alkoxylated alcohol; and optionally a hindered benzoic acid ester, which is more resistant to discoloration due to gas discoloration and thermal oxidation compared to polymer compositions in which the stabilizer composition does not comprise a tertiary HALS stabilizer and an alkoxylated alcohol. Further, a method for manufacturing a stabilized article is provided, the method comprising adding the stabilized polymer composition to a device or method for performing: industrial molding; industrial fiber manufacturing; an industrial tape; and extruding the sheet.

Description

Background Technology

[0001] Many organic materials are known to undergo degradation through several mechanisms, including exposure to electromagnetic radiation such as sunlight and ultraviolet (“UV”) radiation and heat from other sources. For example, as a result of prolonged exposure to the sun, polymeric materials such as plastics often discolor, lose their luster, and become mechanically damaged and / or brittle. Therefore, numerous technologies, such as UV absorbers and various other stabilizers, have been developed to inhibit this degradation in these materials.

[0002] Specifically, UV absorbers such as benzotriazole and benzophenone were initially used to stabilize polymer materials and prevent them from degradation upon exposure to UV rays. It was later discovered that hindered amine light stabilizers (“HALS”), which scavenge free radicals formed in polymer materials when exposed to UV rays, are more effective than UV absorbers (“UVA”). Therefore, it is common practice to use HALS and UV absorbers in combination to stabilize polymer materials.

[0003] For weathering caused by the direct or indirect effects of heat and ultraviolet radiation, the use of UVA on its own or in combination with HALS to stabilize polymers (such as coatings and plastics) remains an active area of ​​research.

[0004] While most stabilizer compositions are intended to reduce or prevent heat-induced degradation, such compositions typically fail to produce the desired results. Frequently, stabilizer compositions intended to reduce or prevent heat-induced degradation are hindered or completely abandoned due to antagonistic effects when combined with compounds that can absorb ultraviolet light.

[0005] It is further known that specific functions of organic materials, such as polymer resins, can be achieved by blending certain additives with these polymer resins. For example, in some cases, it is desirable to modify the surface interface of polymer materials to produce a variety of related surface effects such as improved slip or lubricity, reduced agglomeration, or lubrication of processing equipment. In some cases, it may also be desirable to modify the polymer surface to improve the release of adhesives and promote the release or adhesion of other materials from the surface of the polymer composition. In other cases, polymer films with good clarity and optical properties and resistance to fogging are desirable. Various prior art additives, classified as anti-caking additives, slip agents, coefficient of friction modifiers, antifogging agents, antistatic agents, and release agents, have been used to attempt to impart these properties to different types of organic materials. These different prior art additives are generally described as surface-active compounds (i.e., surfactants).

[0006] Using higher levels of surfactants required to achieve the desired surface effect results in higher costs and often leads to undesirable properties such as blooming and poor processability. Blooming is the process by which polymer articles become supersaturated with these higher levels of surfactants, resulting in the formation of unsightly deposits on the surface of the article.

[0007] Therefore, synergistic combinations of stabilizer additives can still be found, even if these compounds may be known to be used alone for a specific purpose, or to be used together for a specific purpose at concentrations or ratios that have not been previously disclosed or suggested, and do not cause undesirable performance properties such as blooming or poor processability of the organic material to which they are added.

[0008] The discovery of such synergistic stabilizer additives that can significantly improve the performance characteristics of various organic materials subjected to mechanical stress or effects such as oxidation, chain breaking, and uncontrolled recombination and crosslinking reactions (caused by photo-oxidation and heat) would be a useful advance in the field and could be rapidly adopted in many industries that require such stabilized materials. Summary of the Invention

[0009] This summary is provided to illustrate the selection of concepts further described below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

[0010] On the one hand, the embodiments disclosed herein relate to a stable polymer composition comprising an organic polymer material to be stabilized and a stabilizer composition comprising at least one UV absorber selected from the o-hydroxyphenyl-triazine UV absorber class; a secondary hindered amine light stabilizer (sec.-HALS); at least one antioxidant selected from hindered phenols, phosphites, phosphonites, or any mixture thereof; a tertiary hindered amine light stabilizer (tert.-HALS); an alkoxylated alcohol; and optionally a hindered benzoate. This stable polymer composition is more resistant to discoloration due to gas fading and thermal oxidation compared to polymer compositions in which the above-described stabilizer composition does not contain a tertiary HALS stabilizer and an alkoxylated alcohol.

[0011] On the other hand, the embodiments disclosed herein relate to a method for manufacturing stable articles, the method comprising adding a stable polymer composition to an apparatus or method for performing: industrial molding; industrial fiber manufacturing; industrial tape; and extruded sheets.

[0012] Other aspects and advantages of the claimed subject matter will be apparent from the following description and the appended claims. Detailed Implementation

[0013] Stable polymer compositions

[0014] The stabilizer compositions disclosed herein are suitable for stabilizing various organic materials subjected to mechanical stress, discoloration, or effects such as oxidation, chain breaking, and uncontrolled recombination and crosslinking reactions (caused by photo-oxidation), and can be incorporated into such organic materials to protect them from these harmful effects, or can be used as a UV filter layer or within such a filter layer to prevent UV radiation from reaching the organic material or articles made from it.

[0015] The stabilizer compositions according to this disclosure can be readily combined with the organic material to be stabilized by any suitable method known to those skilled in the art, or vice versa. As used herein, the terms "combined" or "combining" relating to the stabilizer composition and the organic material to be stabilized include all methods and / or techniques known to those skilled in the art for intermixing, blending, integrating, mixing, or co-blending two or more substances. In some embodiments, the components of the stabilizer composition can be combined with the material to be stabilized by at least one technique selected from extrusion, granulation, grinding, and molding. In other embodiments, combination can be carried out by at least one of melting, dissolving in a solvent, direct mixing, and dry mixing.

[0016] Incorporating the stabilizer composition according to this disclosure, along with optional additional co-stabilizers and / or co-additives, into the organic material to be stabilized can be done by known methods, such as dry blending in powder form or wet mixing in the form of a solution, dispersion, or suspension (e.g., in an inert solvent, water, or oil). Such stabilizer compositions are preferably non-aqueous. Incorporating the co-activators and UV stabilizers used in the stabilizer composition, along with optional additional co-stabilizers and / or co-additives, into the organic material to be stabilized can be done by any suitable method known to those skilled in the art and includes, for example, before or after molding, or also by applying a dissolved or dispersed stabilizer mixture to the organic material to be stabilized, with or without subsequent evaporation of the solvent or suspension / dispersion. They can be added directly to processing equipment (e.g., extruders, mixers, kneaders, etc.) as dry mixtures or powders, or as solutions, dispersions, suspensions, or melts.

[0017] The individual components of the stabilizer composition according to this disclosure, along with optional additional co-stabilizers and / or co-additives, can also be incorporated into an organic material, such as a polymer, for example, before, during, or immediately after the polymerization of the respective monomers, or at some point before crosslinking. In this context, the stabilizer composition according to this disclosure can also be incorporated into the organic material to be stabilized either in pure form (i.e., pure and added directly to the resin) or encapsulated in waxes, oils, or polymers.

[0018] Various additives can also be pre-blended (i.e., mixed together) for simple addition to the organic material to be stabilized. Individual components of the stabilizer composition, along with optional additional co-stabilizers and / or co-additives, can also be sprayed onto the organic material to be stabilized. These can dilute other conventional additives or their melts, allowing them to also be sprayed onto the material to be stabilized along with these additives. Addition by spraying can be particularly advantageous during the deactivation of any polymerization catalyst, as the released vapors can be used to deactivate the catalyst. In the case of spherically polymerized polymers, for example, it may be advantageous to apply the individual additive components of the stabilizer composition, optionally together with other additives, by spraying.

[0019] Therefore, in one aspect, this disclosure provides a stabilizer composition having a stable amount of an ultraviolet absorber (UVA) selected from the group consisting of: o-hydroxyphenyl triazine compounds; o-hydroxybenzophenone compounds; o-hydroxyphenyl benzotriazole compounds; benzoxazinone compounds; and mixtures thereof; and a co-activator based on 1 wt.% to 99 wt.% of the total weight of the stabilizer composition. In embodiments, the stabilizer composition further comprises a stable amount of both secondary and tertiary hindered amine light stabilizers (HALS); an alkoxylated alcohol; an antioxidant selected from hindered phenols, phosphites, phosphonites, or any mixture thereof; and optionally a hindered benzoate.

[0020] For this reference to the stabilizer compositions disclosed herein as “pure” compositions (i.e., not diluted with or mixed with other substances), the stabilizer compositions may optionally contain additional UV stabilizers, co-stabilizers, and / or co-additives. However, on the other hand, embodiments also include masterbatch concentrates having the stabilizer compositions described in any of the embodiments herein, as well as an organic material that is identical or compatible with the organic material to be stabilized. In this context, the organic material that is identical or compatible with the organic material to be stabilized acts as a carrier for the stabilizer compositions described herein, which is then blended with the organic material to be stabilized. While the amount of stabilizer composition present as part of the total masterbatch concentrate will vary based on, for example, the type of material to be stabilized and / or its end-use application, in some embodiments the stabilizer composition will be present in an amount from 10 wt.% to 90 wt.% based on the total weight of the masterbatch concentrate. In other embodiments, the stabilizer composition may be present in an amount from 30 wt.% to 80 wt.%; or 40 wt.% to 75 wt.% of the total weight of the masterbatch concentrate.

[0021] stabilizer composition

[0022] As discussed above, the stabilizer composition according to one or more embodiments comprises an ultraviolet absorber (UVA) selected from the group consisting of: o-hydroxyphenyl triazine compounds, o-hydroxybenzophenone compounds, o-hydroxyphenyl benzotriazole compounds, benzoxazinone compounds, and mixtures thereof; secondary and tertiary hindered amine light stabilizers (HALS); alkoxylated alcohols; antioxidants selected from hindered phenols, phosphites, phosphonites, or any mixture thereof; and optionally hindered benzoates.

[0023] UV absorber

[0024] Regarding UV stabilizer systems for stabilizer compositions, o-hydroxyphenyltriazine is a class of effective triazines used in stabilizer compositions.

[0025] o-Hydroxyphenyl triazines are well known in the art and in the field of stabilizer additive technology. They have been disclosed and discussed in numerous references and patents, including U.S. Patent Nos. 6,051,164 and 6,843,939, wherein o-hydroxyphenyl triazine compounds are incorporated herein by reference. Particularly preferred o-hydroxyphenyl triazines include 2-(2'-hydroxyphenyl)-1,3,5-triazine compounds according to formula (I):

[0026]

[0027] (I)

[0028] in

[0029] R 34 and R 35 Same or different and selected independently from:

[0030] C6-C 10 Aryl, wherein the C6-C 10 The aryl group is optionally substituted at one to three substituted positions by one or more groups selected from the following: OH, halogen, C1-C. 12 Alkyl, C1-C 12 Alkoxy, C1- 12 Alkoxy esters, C 2-12 Alkyl, or phenyl, wherein the phenyl group is optionally substituted at one to three substituted positions with one or more groups selected from: hydroxyl, halogen, C 1-12 Alkyl, C 1-12 Alkoxy, C 1-12 alkoxy esters, or C 2-12 Alkyl group;

[0031] Single or double C1-C 12 Hydroxyl-substituted amino groups;

[0032] C2-C 12 Alkyl group;

[0033] C1-C 12 alkyl;

[0034] C1-C 10 Acyl group; or

[0035] C1-C 10 alkoxy groups; and

[0036] R 36 It consists of identical or different substituents at positions 0 to 4 of the phenoxy moiety in formula (I), and is independently selected from hydroxyl, halogen, C1-C... 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxy esters, C2-C 12 Alkyl; phenyl; or C1-C 12 Acyl group.

[0037] Commercially available o-hydroxyphenyl triazines include, but are not limited to, those under the trade names CYASORB® UV-1164 (available from Cytec Industries Inc., Woodland Park, New Jersey); TINUVIN® 1577FF; or TINUVIN® 400 (available from BASF, Ludwigshafen, Germany). In some embodiments, the o-hydroxyphenyl triazine compound of the stabilizer composition includes, but is not limited to, one or more of the following compounds:

[0038] 4,6-Bis-(2,4-Dimethylphenyl)-2-(2-hydroxy-4-octoxyphenyl)-triazine;

[0039] 2-(4,6-Diphenyl-1,3,5-triazine-2-yl-)-5-((hexyl)oxy-phenol;

[0040] 4,6-Bis-(2,4-dimethylphenyl)-2-(2,4-dihydroxyphenyl)-triazine;

[0041] 2,4-Bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-triazine;

[0042] 2,4-Bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-triazine (TRIAZINE™ 460);

[0043] 2,4-Bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(4-chlorophenyl)-triazine;

[0044] 2,4-Bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]-6-(2,4-dimethylphenyl)-triazine;

[0045] 2,4-Bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-bromophenyl)-triazine;

[0046] 2,4-Bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-triazine;

[0047] 2,4-Bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-triazine;

[0048] 2,4-Bis(4-biphenyl)-6-[2-hydroxy-4-[(octoxycarbonyl)ethoxy]phenyl]-triazine;

[0049] 2,4-Bis(4-biphenyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-triazine;

[0050] 2-Phenylacetyl-4-[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)phenyl]-6-[2-hydroxy-4-(3-sec-pentoxy-2-hydroxypropoxy)phenyl]-triazine;

[0051] 2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(-3-benzyloxy-2-hydroxypropoxy)phenyl]-triazine;

[0052] 2,4-Bis(2-hydroxy-4-n-butoxyphenyl)-6-(2,4-di-n-butoxyphenyl)-triazine;

[0053] 2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonoxy-2-hydroxypropoxy)-5-α-cumylphenyl]-triazine;

[0054] 2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-[(octoxycarbonyl)ethoxy]phenyl]-triazine (TINUVIN™ 479);

[0055] Methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-triazine;

[0056] A mixture of methylene-bridged dimers bridged at the 3:5', 5:5' and 3:3' positions in a 5:4:1 ratio;

[0057] 2,4,6-Tris(2-hydroxy-4-isooctyloxycarbonyliso-propoxy-phenyl)-triazine;

[0058] 2,4,6-Tris[2-hydroxy-4-[(octoxycarbonyl)ethoxy]phenyl]-triazine (TINUVIN™ 477);

[0059] 2,4,6-Tris(2-hydroxy-4-octyloxy-phenyl)-1,3,5-triazine;

[0060] 2,4-Bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α-cumylphenyl)-triazine;

[0061] 2,4-Bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-triazine;

[0062] 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-triazine;

[0063] 2,4,6-Tris[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)-phenyl]-triazine;

[0064] A mixture of 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)phenyl)-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tetratekoxy-2-hydroxypropoxy)phenyl)-triazine;

[0065] 4,6-Bis-(2,4-Dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-triazine;

[0066] 4,6-Bis-(2,4-Dimethylphenyl)-2-(2-hydroxy-4-isooctyloxyphenyl)-triazine (CYASORB™UV-1164L); or

[0067] 4,6-Diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-triazine.

[0068] Other UVA compounds suitable for use in the compositions described herein include one or more of o-hydroxybenzophenone, o-hydroxyphenylbenzotriazole, oxaloaniline, cyanoacrylate, or benzoxazinone compounds. In some embodiments, the UVA component of the stabilizer composition comprises individually o-hydroxytriazine, o-hydroxybenzophenone, o-hydroxyphenylbenzotriazole, or benzoxazinone. In other embodiments, the UVA component comprises a combination of two or more of these UVA compounds. O-hydroxybenzophenone, o-hydroxybenzotriazole, and benzoxazinone are also well known to those skilled in the art of stabilizer additives. The suitability of their use as components of stabilizer compositions has been previously disclosed and discussed in at least the following U.S. Patent Nos. 2,976,259; 3,049,443; 3,399,169; 4,322,455; 4,446,262; 5,264,539; 6,051,164; 6,677,392; and 6,774,232, as well as U.S. Publication No. 2006 / 0052491, wherein benzophenone, benzotriazole, and benzoxazinone, by reference herein, are suitable for use with the stabilizer compositions disclosed herein.

[0069] Other non-limiting examples of o-hydroxybenzophenone or 2-hydroxybenzophenone for use with the stabilizer compositions contemplated herein include any one or more of the following: 2-hydroxy-4-methoxybenzophenone (commercially available from Cytec Industries as CYASORB® UV-9); 2,2'-dihydroxy-4-methoxybenzophenone (commercially available from Cytec Industries as CYASORB® UV-24); 2-hydroxy-4-octyloxybenzophenone (commercially available from Cytec Industries as CYASORB® UV-531 is commercially available); 2,2'-dihydroxy-4,4'-di-methoxybenzophenone; 2,2'-dihydroxybenzophenone; 2,2',4,4'-tetrahydroxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; 2,2'-dihydroxy-4,4'-diethoxybenzophenone; 2,2'-dihydroxy-4,4'-dipropoxybenzophenone; 2,2'-dihydroxy-4,4'-dibutoxybenzophenone; 2,2'-dihydroxy-4,4'-diethoxybenzophenone; 2,2'-dihydroxy-4,4'-dipropoxybenzophenone; 2,2'-dihydroxy-4,4'-dibutoxybenzophenone; 2,2'-dihydroxy-4,4'-dimethoxy-4'-ethoxybenzophenone; 2,2'-dihydroxy-4,4'-dipropoxybenzophenone; 2,2'-Dihydroxy-4-methoxy-4'-butoxybenzophenone; 2,2'-Dihydroxy-4-ethoxy-4'-propoxybenzophenone; 2,2'-Dihydroxy-4-ethoxy-4'-butoxybenzophenone; 2,3'-Dihydroxy-4,4'-dimethoxybenzophenone; 2,3'-Dihydroxy-4-methoxy-4'-butoxybenzophenone; 2-Hydroxy-4,4',5'-trimethoxybenzophenone; 2-Hydroxy-4,4',6'-tributoxybenzophenone; 2-Hydroxy-4-butoxy-4',5'-dimethoxybenzophenone; 2-Hydroxy-4-ethoxy-2',4'-dibutylbenzophenone; 2-Hydroxy-4-propoxy-4',6'-dichlorobenzophenone; 2-Hydroxy-4-propoxy-4',6'-dibromobenzophenone; 2,4-dihydroxybenzophenone; 2-Hydroxy-4-ethoxybenzophenone; 2-Hydroxy-4-propoxybenzophenone; 2-Hydroxy-4-butoxybenzophenone; 2-Hydroxy-4-methoxy-4'-methylbenzophenone; 2-Hydroxy-4-methoxy-4'-ethylbenzophenone; 2-Hydroxy-4-methoxy-4'-propylbenzophenone; 2-Hydroxy-4-methoxy -4'-Butylbenzophenone; 2-Hydroxy-4-methoxy-4'-tert-butylbenzophenone; 2-Hydroxy-4-methoxy-4'-chlorobenzophenone; 2-Hydroxy-4-methoxy-2'-chlorobenzophenone; 2-Hydroxy-4-methoxy-4'-bromobenzophenone; 2-Hydroxy-4,4'-dimethoxybenzophenone; 2-Hydroxy-4,4'-dimethoxy-3-methylbenzophenone; 2-Hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone; 2-Hydroxy-4,4',5'-trimethoxybenzophenone; 2-Hydroxy-4-ethoxy-4'-methylbenzophenone;2-Hydroxy-4-ethoxy-4'-ethyl benzophenone; 2-Hydroxy-4-ethoxy-4'-propyl benzophenone; 2-Hydroxy-4-ethoxy-4'-butyl benzophenone; 2-Hydroxy-4-ethoxy-4'-methoxy benzophenone; 2-Hydroxy-4,4'-diethoxy benzophenone; 2-Hydroxy-4-ethoxy-4'-propoxy benzophenone; 2-Hydroxy-4-ethoxy-4'-butoxy benzophenone; 2-Hydroxy-4-ethoxy-4'-chlorobenzophenone; or 2-Hydroxy-4-ethoxy-4'-bromobenzophenone.

[0070] Some other non-limiting examples of useful o-hydroxyphenylbenzotriazoles in the UVA component of the stabilizer compositions described herein include one or more of the following: those commercially available from Cytec Industries (e.g., CYASORB®UV-5411), or 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)-benzotriazole; 2-(2'-hydroxy-5'-cyclohexylphenyl)-benzotriazole; 2-(2'-hydroxy-3',5'-dimethylphenyl)-benzotriazole; 2-(2'-hydroxy- 5'-tert-butylphenyl)-5-chlorobenzotriazole; 2-(2'-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5-octylphenyl)-2H-benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole; 2-(3',5'-di-tert-pentyl-2'-hydroxyphenyl)benzotriazole (from Cytec Industries as CYASORB®) UV-2337 is commercially available); 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole; 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octoxycarbonylethyl)phenyl)benzotriazole; 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; 2-[2 [-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-butyl)phenyl]benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole; 2-(2'-hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole; 2-(2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole; 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole (TINUVIN™) 326); 2-(3'-tert-butyl-5'-methyl-2'-hydroxyphenyl)-5-chloro-benzotriazole; 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-benzotriazole; 2-(5'-tert-octyl-2'-hydroxyphenyl)-benzotriazole; 2-(3'-dodecyl-5'-methyl-2'-hydroxyphenyl)-benzotriazole; 2-(3'-tert-butyl-5'-(2-octoxycarbonylethyl)-2'-hydroxyphenyl)-5-chlorobenzotriazole; 2-(5'-methyl-2'-hydroxyphenyl)-benzotriazole; 2-(5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole;Or 2-(2'-hydroxy-3'-di-tert-butylphenyl)-benzotriazole.

[0071] Non-limiting examples of benzoxazinones useful in the UVA portion of the stabilizer compositions described herein include one or more selected from the group consisting of: 2-methyl-3,1-benzoxazin-4-one; 2-butyl-3,1-benzoxazin-4-one; 2-phenyl-3,1-benzoxazin-4-one; 2-(1- or 2-naphthyl)-3,1-benzoxazin-4-one; 2-(4-biphenyl)-3,1-benzoxazin-4-one; 2-p-nitrophenyl-3,1-benzoxazin-4-one; 2-m-nitrophenyl-3,1-benzoxazin-4-one; 2-p-benzoylphenyl-3,1-benzoxazin-4-one; 2-p-methoxyphenyl-3,1-benzoxazin-4-one; 2-o- Methoxyphenyl-3,1-benzoxazin-4-one; 2-cyclohexyl-3,1-benzoxazin-4-one; 2-p-(or m-)phthalimide phenyl-3,1-benzoxazin-4-one; N-phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide; N-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline; N-benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline; 2-[p-(N-phenylcarbamoyl)phenyl]-3,1-benzoxazin-4-one; 2-[p-(N-phenylN-methylcarbamoyl)phenyl]-3,1-benzoxazin-4-one; 2,2'-bis(phenyl-N-methylcarbamoyl)phenyl]-3,1-benzoxazin-4-one; (3,1-Benzoxazin-4-one); 2,2'-Ethylenebis(3,1-Benzoxazin-4-one); 2,2'-Tetramethylenebis(3,1-Benzoxazin-4-one); 2,2'-Hexamethylenebis(3,1-Benzoxazin-4-one); 2,2'-Decamethylbis(3,1-Benzoxazin-4-one); 2,2'-p-Phenylidenebis(3,1-Benzoxazin-4-one); 2,2'-m-Phenylidenebis(3,1-Benzoxazin-4-one); 2,2'-(4,4'-Diphenylene)bis(3,1-Benzoxazin-4-one); 2,2'-(2,6- or 1,5-naphthalene)bis(3,1-Benzoxazin-4-one); 2,2'-(2-methyl-p-phenylene)bis(3,1-Benzoxazin-4-one) 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one); 2,2'-(1,4-cyclohexene)bis(3,1-benzoxazin-4-one); N-p-(3,1-benzoxazin-4-one-2-yl)phenyl; 4-(3,1-benzoxazin-4-one-2-yl)phthalimide; N-p-(3,1-benzoxazin-4-one-2-yl)benzoyl; 4-(3,1-benzoxazin-4-one-2-yl)aniline; 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)benzene;1,3,5-Tris(3,1-benzoxazin-4-one-2-yl)naphthalene; or 2,4,6-Tris(3,1-benzoxazin-4-one-2-yl)naphthalene.

[0072] UV absorbers may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.% or 0.1 wt.% to an upper limit of 0.25 wt.%, 0.5 wt.% or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0073] Inorganic UV blocking agent

[0074] The stabilizer composition according to one or more embodiments may further comprise an inorganic UV blocker. Suitable inorganic UV blockers may be titanium oxide, zinc oxide, cerium oxide, barium sulfate, or any combination thereof. The inorganic UV blocker may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, or 1.0 wt.% to an upper limit of 1.0, 2.0, 3.0, 4.0, or 5.0 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0075] Hindered amine light stabilizers (HALS)

[0076] As previously discussed, HALS compounds scavenge free radicals formed in polymeric materials upon exposure to UV rays, and are more effective as a combination of secondary and tertiary HALS than when UVA is used with HALS alone. The benefits imparted by various HALS compounds in combination with UVA have been demonstrated in at least U.S. Patent Nos. 6,051,164 and 6,843,939, the teachings of which are incorporated herein by reference. Therefore, in some embodiments, the stabilizer compositions described herein comprise a stable amount of at least one secondary HALS compound and at least one tertiary HALS compound containing a functional group according to formula (II):

[0077]

[0078] in

[0079] R 31 Selected from: hydrogen (for secondary HALS); or (for tertiary HALS) OH; C1-C 20 Hydrocarbon group; —CH2CN; C1-C 12 Acyl group; or C1-C 18 Alkoxy;

[0080] R 38Selected from: hydrogen; or C1-C8 hydrocarbon groups; and

[0081] R 29 R 30 R 32 and R 33 Each of them is independently selected from C1-C 20 hydrocarbon group, or R 29 and R 30 and / or R 32 and R 33 Together with the carbon attached to them, they form C5-C 10 cycloalkyl; or

[0082] According to the functional group of formula (IIa):

[0083]

[0084] in

[0085] m is an integer from 1 to 2;

[0086] R 39 Selected from: hydrogen; OH; C1-C 20 Hydrocarbon group; —CH2CN; C1-C 12 Acyl group; or C1-C 18 alkoxy groups; and

[0087] Each of G1-G4 is independently selected from C1-C 20 Hydrocarbon group.

[0088] Exemplary HALS compounds contemplated for use as components in the stabilizer compositions described herein may include one or more of the following: those commercially available from Cytec Industries, such as mixtures of 4-hexadecyloxy- and 4-stearoxy-2,2,6,6-tetramethylpiperidine (e.g., CYASORB® UV-3853), or bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate; bis(2,2,6,6-tetramethylpiperidine-4-yl) succinate; bis(1,2,2,6,6-pentamethylpiperidine-4-yl) sebacate; bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate; bis(1,2,2,6,6-pentamethylpiperidine-4-yl) sebacate. -4-yl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate; condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; 2,2,6,6-tetramethylpiperidine-4-yl stearate; 2,2,6,6-tetramethylpiperidine-4-yl dodecanoate; 1,2,2,6,6-pentamethylpiperidine-4-yl stearate; dodecanoate 1,2,2,6,6-pentamethylpiperidin-4-yl ester of alkyl ester; condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of hypoazine triacetate; tetra(2,2,6,6-tetramethylpiperidin-4-yl)-1,2 ,3,4-Butanetetracarboxylate; 4-benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearoyl-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4].5] Dec-2,4-dione; bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) sebacate; bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) succinate; condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine (commercially available from Cytec Industries as CYASORB® UV-3346); methylated condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine (commercially available from Cytec Industries as CYASORB® UV-3529 is commercially available; a condensation of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; a condensation of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane; 8-acetyl -3-Dodecyl-7,7,9,9-Tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione; 3-Dodecyl-1-(2,2,6,6-Tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-Dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-Dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione A mixture of pyridine-4-yl)pyrrolidine-2,5-dione; a mixture of 4-hexadecyloxy- and 4-stearoyloxy-2,2,6,6-tetramethylpiperidine; a mixture of 4-hexadecyloxy- and 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine; a condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; 1,2-bis A condensation of (3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperazinyl-triazine; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane; oxo-piperazinyl-triazine; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane.5] The reaction product of decane and epichlorohydrin; tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)butane-1,2,3,4-tetracarboxylate; tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester of 1,2,3,4-butanetetracarboxylate; 1,2,2,6,6-pentamethyl-4-piperidinyltridecyl ester of 1,2,3,4-butanetetracarboxylate; 2,2,6,6-tetramethyl-4-piperidinyltridecyl ester of 1,2,3,4-butanetetracarboxylate; 1,2,3,4-butanetetracarboxylate and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]-undecane-3,9-diethanol, 1,2,2, Polymers of 6,6-pentamethyl-4-piperidinyl esters; polymers of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxazolo[5.5]-undecane-3,9-diethanol and 2,2,6,6-tetramethyl-4-piperidinyl esters; bis(1-undecoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate; 1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-piperidinol; 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin; 1-(4-octadecanoyloxy-2,2,6,6-tetramethylpiperidinol) Methylpiperidin-1-yloxy)-2-octadecanoyloxy-2-methylpropane; 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol; the reaction product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and dimethyl succinate; 2,2,4,4-tetramethyl-7-oxa-3,20-diazabispiro[5.1.11.2]eicosano-21-one; esters of 2,2,6,6-tetramethyl-4-piperidinol with higher fatty acids; 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidine-2,5-dione; 1-octadecyl-1H-pyrrole-2,5-di Polymers of ketones with (1-methylvinyl)benzene and 1-(2,2,6,6-tetramethyl-4-piperidinyl)-1H-pyrrole-2,5-dione; 1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl]]tris[3,3,5,5-tetramethyl-piperazinone; 1,1',1''-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl]]tris[3,3,4,5,5-pentamethyl-piperazinone; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5] The reaction product of decane and epichlorohydrin; a condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; a condensation product of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butano-2,2,6,6-tetramethylpiperidin; a condensation product of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine Condensations of aziridine and 1,2-bis(3-aminopropylamino)ethane; condensations of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane; 2-[(2-hydroxyethyl)amino]-4,6-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butano-1,3,5-triazine; malonate [(4-methoxyphenyl)-methylene]-bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; tetra(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy-, 1-[2-[3-[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]-1-oxopropoxy]ethyl]-2,2,6,6-tetramethyl-4-piperidinyl ester; N-(1-octoxy-2,2,6,6-tetramethylpiperidin-4-yl)-N'-dodecyloxalamide; tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of hypoazine triacetate; bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester of 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid; bis(2,2,6,6-tetramethyl-4-piperidinyl) ester of 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid; bis(2,2,6,6-tetramethyl-4-piperidinyl) ester of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidinyl Condensations of pyridine and succinic acid; condensations of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro1,3,5-triazine; 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4-piperidinyltridecyl ester; tetra(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylic acid 2,2,6,6-tetramethyl-4-piperidinyltridecyl ester; tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylic acid 2,2,6,6-tetramethyl-4-piperidinyltridecyl ester; tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylic acid 2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazaspiro(5).A mixture of (1.11.2)-cuicosanoid-20-propionic acid-dodecyl ester and 2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazaspiro(5.1.11.2)-cuicosanoid-20-propionic acid-tetradecyl ester; hexahydro-2,6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1H,4H,5H,8H-2,3a,4a,6,7a,8a-hexaaza Cyclopentanylfluorene-4,8-dione; polymethyl[propyl-3-oxy(2',2',6',6'-tetramethyl-4,4'-piperidinyl)]siloxane; polymethyl[propyl-3-oxy(1',2',2',6',6'-pentamethyl-4,4'-piperidinyl)]siloxane; copolymer of methyl methacrylate with ethyl acrylate and 2,2,6,6-tetramethylpiperidin-4-yl acrylate; mixed C. 20 To C 24Copolymers of α-olefins and (2,2,6,6-tetramethylpiperidin-4-yl)succinimide; polymers of 1,2,3,4-butanetetracarboxylic acid with β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol and 1,2,2,6,6-pentamethyl-4-piperidinyl ester; 1,2,3,4-butanetetracarboxylic acid with β ,β,β',β'-Tetramethyl-2,4,8,10-tetraoxazolo[5.5]undecane-3,9-diethanol, 2,2,6,6-tetramethyl-4-piperidinyl ester copolymer; N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)1,3-phenylenediamide; 1,1'-(1,10-dioxo-1,10-decanediyl)-bis(hexadecanediyl) Hydrogen-2,2,4,4,6-pentamethylpyrimidine; N-(1-acetyl-2,2,6,6-tetramethylpiperidinyl)-N'-dodecylethanediamide; N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl)formamide; 1,3:2,4-bis-O-(2,2,6,6-tetramethyl-4-piperidinyl)-D-glucose Glucoside; 2,2,4,4-Tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]eicosane; 2-Methyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)-2-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]-propionamide; 7-oxa-3,20-diaza-dispiro[5.1.11.2] Docosano-20-propionic acid, 2,2,4,4-tetramethyl-21-oxo-, dodecyl ester; N-(2,2,6,6-tetramethylpiperidin-4-yl)-β-aminopropionic acid dodecyl ester; N-(2,2,6,6-tetramethylpiperidin-4-yl)-N'-aminooxalamide; N-(2,2,6,6-tetramethyl-4-piperidinyl)-3-[(2,2,6,6-tetramethyl-4-piperidinyl)amino]-propionamide; a mixture of 4-hexadecyloxy- and 4-stearoyloxy-2,2,6,6-tetramethylpiperidine; 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1-acetyl-2-dione) 2,6,6-Pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate; tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of hypoazine triacetate; 1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone); 4-benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearoyl-2,2,6,6-tetramethylpiperidine; bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy 3-Octyl-3,5-di-tert-butylbenzyl)malonate; 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione; bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) sebacate; bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) succinate; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]dec-2,4-dione; 3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidinyl) Pyridine-4-yl)pyrrolidine-2,5-dione; 3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione; a mixture of 4-hexadecoxy- and 4-stearooxy-2,2,6,6-tetramethylpiperidine; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane; 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid bis(2,2,6,6-tetramethyl-4-piperidinyl) ester and 1,5-dioxaspiro{5,5}undecane-3,3-dicarboxylic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; N. 1 -(β-hydroxyethyl)3,3-pentamethylene-5,5-dimethylpiperazin-2-one; N1 -tert-octyl-3,3,5,5-tetramethyl-diaza-2-one; N 1 -tert-octyl-3,3-pentamethylene-5,5-hexamethylene-diaza-2-one; N 1 -tert-octyl-3,3-pentamethylene-5,5-dimethylpiperazin-2-one; trans-1,2-cyclohexane-bis-(N 1 -5,5-dimethyl-3,3-pentamethylene-2-piperazinone); trans-1,2-cyclohexane-bis-(N 1 -3,3,5,5-Dispiropyramethylene-2-piperazinone); N 1 -Isopropyl-1,4-diazabispiro-(3,3,5,5)pentamethylene-2-piperazinone; N 1 -Isopropyl-1,4-diazabispiro-3,3-pentamethylene-5,5-tetramethylene-2-piperazinone; N 1 -Isopropyl-5,5-dimethyl-3,3-pentamethylene-2-piperazinone; trans-1,2-cyclohexane-bis-N 1 -(dimethyl-3,3-pentamethylene-2-piperazinone); N 1 -Octyl-5,5-dimethyl-3,3-pentamethylene-1,4-diaza-2-one; N 1 -Octyl-1,4-diazabispiro-(3,3,5,5)pentamethylene-1,5-diazabispiro-2-one; TINUVIN®XT 200 (available from BASF); or TINUVIN ® NOR 371 (available from BASF).

[0089] Secondary hindered amine light stabilizers (sec.-HALS)

[0090] Preferred secondary hindered amine light stabilizers (sec.-HALS) It can be selected from bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate; C 12 -C 21 Saturated fatty acids and C 18A mixture of 2,2,6,6-tetramethylpiperidin-4-yl esters of unsaturated fatty acids (CYASORB™ UV-3853); bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate (Tinuvin 770); 2,2,6,6-tetramethylpiperidin-4-yl stearate; 2,2,6,6-tetramethylpiperidin-4-yl dodecanoate; a condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine (CHIMASSORB™ 944); tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of azidotriacetate; 4-stearoyloxy-2,2,6,6-tetramethylpiperidine; condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine (CYASORB™ UV-3346); condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, di-n-butylamine and 2,4,6-trichloro-1,3,5-triazine (CHIMASSORB™ 2020); condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; condensate of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; Condensation of methylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; tetra(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; 2,2,6,6-tetramethylpiperidin-4-yltridecyl ester of 1,2,3,4-butanetetracarboxylate; N,N'-1,6-hexadiylbis[N-(2,2,6,6-tetramethylpiperidin-4-yl)carboxamide (UVINUL™ 4050).

[0091] Secondary hindered amine light stabilizers (sec.-HALS) may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.% or 0.1 wt.% to an upper limit of 2.5 wt.%, 5 wt.% or 10 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0092] Tertiary hindered amine light stabilizers (tert.-HALS)

[0093] Preferred tertiary hindered amine light stabilizers (tert.-HALS)It can be selected from bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethyl-4-piperidinyl); bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4-hydroxybenzyl malonate; a condensation of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; a mixture of bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate and methyl 1,2,2,6,6-pentamethylpiperidin-4-yl sebacate (TINUVIN™) 292); bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-hydroxybenzyl malonate; condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid (TINUVIN™ 622); 1,2,2,6,6-pentamethylpiperidin-4-yl stearate; 1,2,2,6,6-pentamethylpiperidin-4-yl dodecanoate; methylated condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine (CYASORB™ UV-3529; a condensate of 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane; tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; a mixture of 4-hexadecyloxy- and 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidine; 1,5,8,12-tetra[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane (Chimassorb) 119); Polymer of 1,2,3,4-butanetetracarboxylic acid with β,β,β′-tetramethyl-2,4,8,10-tetraoxyspiro[5,5]undecane-3,9-diethanol and 1,2,2,6,6-pentamethyl-4-piperidinyl ester (ADK STAB LA63).

[0094] Tertiary hindered amine light stabilizers (tert.-HALS) may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, or 0.1 wt.% to an upper limit of 2.5 wt.%, 5 wt.%, or 10 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0095] The weight ratio of sec.-HALS to tert.-HALS can vary depending on the components in the composition, the type of material to be stabilized, and / or the application of the stabilizing material. In one or more embodiments, the ratio of sec.-HALS to tert.-HALS can be in the form of 10:1 to 1:10, 8:1 to 1:8, 5:1 to 1:5, or 2:1 to 1:2 by weight.

[0096] Alkoxylated alcohols

[0097] The stabilizer composition according to one or more embodiments comprises an alkoxylated alcohol. In some embodiments, the alkoxylated alcohol is according to formula (III):

[0098] R—(OCHR'CH2) y —OR” (III)

[0099] Where R is a hydrocarbon group having 12 to 60 carbon atoms; R' is selected from H or C1-C4 alkyl; R” is selected from H; and y is an integer from 1 to 100.

[0100] As used herein, the term "hydrocarbon group" is a general term for aliphatic, alicyclic, and aromatic groups having a full carbon skeleton and consisting of carbon and hydrogen atoms. In some cases, as defined herein, one or more carbon atoms constituting the carbon skeleton may optionally be replaced or interrupted by specific atoms or groups of atoms such as one or more heteroatoms of N, O, and / or S. Examples of hydrocarbon groups include alkyl, cycloalkyl, cycloalkenyl, carbocyclic aryl, alkenyl, ynylcycloalkyl, cycloalkylalkyl, cycloalkenylalkyl, and carbocyclic arylalkyl, alkylaryl, arylenyl, and aryynyl.

[0101] Such hydrocarbon groups may also be optionally substituted by one or more substituents as defined herein. Unless the context otherwise indicates, the examples and preferences shown below also apply to each of the hydrocarbon substituents or hydrocarbon-containing substituents referred to in the various definitions of substituents of compounds having the formula described herein.

[0102] Preferred non-aromatic hydrocarbon groups are saturated groups, such as alkyl and cycloalkyl groups. Generally, and by way of example, hydrocarbon groups can have up to one hundred carbon atoms, unless the context requires otherwise. Hydrocarbon groups having 1 to 60 carbon atoms are preferred, and those having 1 to 36 carbon atoms are more preferred. Within a subset of hydrocarbon groups, a specific example is C... 12-60 hydrocarbon group, C 12-30 hydrocarbon group, C 12-22 hydrocarbon group, C 1-10 hydrocarbon group, or C 1-4 Hydrocarbon groups, although selected from C1 to C2 60Any single value, range, or combination of values ​​of the hydrocarbon group is conceived by the inventors, as specifically listed herein.

[0103] As indicated by the context in which it is used herein, the term "alkyl" is intended to include straight-chain, branched, or cyclic hydrocarbon structures and combinations thereof. Lower alkyl groups refer to alkyl groups having 1 to 6 carbon atoms. Examples of lower alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl, pentyl, hexyl, or cyclohexyl, etc. Preferred alkyl groups include C14 and C24. 36 or below C 36 Those.

[0104] Therefore, in some embodiments, R having formula (III) can be an alkyl group having 12 to 30 carbon atoms. In other embodiments, R can contain 12 to 22 carbon atoms, and ideally 12 to 18 carbon atoms, or 12 to 15 carbon atoms.

[0105] As used herein, the terms "alkoxy," "alkoxyalkyl," or "alkoxylated" refer to a group of 1 to 20 carbon atoms in a straight-chain, branched, or cyclic configuration or a combination thereof, which is attached to the parent structure via an oxygen atom or bonded to a portion of the main chain via an oxygen atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, cyclopropoxy, cyclohexyloxy, etc.

[0106] Therefore, in some embodiments, or in the same embodiments as those previously described with respect to formula (III), R' may be methyl or ethyl. In other embodiments, R' may be H.

[0107] Therefore, in some embodiments, the stabilizer composition according to this disclosure may comprise a co-activator that can be alkoxylated with one or more alkoxides. In some embodiments, the co-activator according to formula (III) may be ethoxylated. In other embodiments, the co-activator according to formula (III) may be propoxylated. In the same or other embodiments, the co-activator according to formula (III) may comprise a mixture of ethoxylated alcohols and propoxylated alcohols, or may be an alcohol that ethoxylates and propoxylates both.

[0108] While the degree of alkoxylation (i.e., the number of ethoxy and / or propoxy groups in the co-activator) can vary in the co-activator, the inventors have conceived of a degree of alkoxylation range of 1 to 100 for the co-activators described herein. In some embodiments, the degree of alkoxylation of the co-activator according to formula (III) may be in the range of 1 to 75, given by "y". In other embodiments, the degree of alkoxylation may be in the range of 2 to 25, or 2 to 12.

[0109] In any embodiment of the co-activator according to formula (III) as discussed above, the co-activator may be an alcohol, such as when R” is H.

[0110] Although alkoxylated alcohols according to formula (III) can be prepared by known methods that are available to those skilled in the art, there is a large number of such compounds that are currently commercially available. Such commercially available alkoxylated compounds include, but are not limited to, any of the commercially available or known alkoxylated alcohols under the trade name BRIJ® (available from Sigma Aldrich, St. Louis, MO); JEECOL® (available from Jeen Int'l Corp.); NOVEL® (available from Sasol Olefins & Surfactants, Hamburg, Germany); UNITHOX® ethoxylates (available from Baker Hughes, Inc.); GENAPOL® (available from Clariant SE, Switzerland); HETOXOL® (available from Global Seven, Rockaway, NJ); and LEUNAPON® (available from Vantage Leuna, Germany). Although these compounds can generally be in any form (i.e., liquid, solid, semi-solid, flake, tablet), solid or semi-solid forms are preferred.

[0111] In some embodiments, the alkoxylated alcohol may be selected from any one or more of the following: diethylene glycol octadecyl ether (available as BRIJ® S2); triethylene glycol octadecyl ether (available as BRIJ® S3); polyoxyethylene (5) octadecyl ether (available as Steareth-5); polyoxyethylene (10) octadecyl ether (available as JEECOL® SA-10); polyoxyethylene (2) oleyl ether (available as BRIJ® 93); polyoxyethylene docosyl ether (available as NOVEL® 22-4); polyoxyethylene (4) oleyl ether (available as HETOXOL® OL-4) or LEUNAPON™ F1618-55 (C 16 -C 18 Alkyl alcohol ethoxylates).

[0112] Alkoxylated alcohols may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.001 wt.%, 0.01 wt.%, 0.05 wt.% or 0.1 wt.% to an upper limit of 0.25 wt.%, 0.5 wt.% or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0113] The weight ratio of tert.-HALS to alkoxylated alcohols can vary depending on the components in the composition, the type of material to be stabilized, and / or the application of the stabilizing material. In examples, the ratio of tert.-HALS or sec.-HALS to alkoxylated alcohols can be in the form of 100:1 to 1:1, 50:1 to 25:1, or 10:1 to 5:1 by weight.

[0114] Co-additives

[0115] Suitable co-additives can be nucleating agents, fillers, metal stearates, reinforcing agents, plasticizers, lubricants, rheology modifiers, catalysts, leveling agents, optical brighteners, antistatic agents, foaming agents, flame retardants, dyes, pigments, hindered benzoates, thioesters, hydroxylamines, antioxidants, hindered phenols, phosphites, phosphonites, benzofuranones, nitrones, and mixtures thereof. Examples of such co-additives include, but are not limited to, any one of those disclosed in U.S. Publications 2004 / 0152807; 2009 / 0085252; 2012 / 0146257; and 2013 / 0145962, which are expressly incorporated herein by reference or are known to those skilled in the art.

[0116] Co-additives may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, or 1 wt.% to an upper limit of 1, 2, 3, 4, 5, 10, or 20 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0117] Hindered benzoates or benzamides

[0118] Suitable hindered benzoates or benzamides for use with the UVA portion of a stabilizer composition include those according to formula (VI):

[0119] (VI)

[0120] in

[0121] R 21 and R 22 Each of them is independently selected from C 1-12 alkyl;

[0122] T is selected from O or NR 24 , where R 24 Is it H or C? 1-30 hydrocarbon group; and R 23 Is it H or C? 1-30 Hydrocarbon group.

[0123] Preferred hindered benzoate esters may include any one or more of the following: those commercially available from Cytec Industries, such as hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate (e.g., CYASORB®). UV-2908), or 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4-hydroxybenzoate; decyl-3,5-di-tert-butyl-4-hydroxybenzoate; dodecyl-3,5-di-tert-butyl-4-hydroxybenzoate; tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; betainol-3,5-di-tert-butyl-4-hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; or butyl-3-[3-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxybenzoyloxy)phenyl]propionate.

[0124] Hindered benzoate and / or benzamide may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, or 0.1 wt.% to an upper limit of 0.25 wt.%, 0.5 wt.%, or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0125] hydroxylamine

[0126] Preferred hydroxylamines include, but are not limited to, any one or more selected from the following N,N-dialkylhydroxylamines: N,N-dibenzylhydroxylamine; N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine; N,N-dilaurylhydroxylamine; N,N-bis(dodecylhydroxylamine); N,N-bis(tetradecylhydroxylamine); N,N-bis(hexadecylhydroxylamine); N,N-bis(octadecylhydroxylamine); N-hexadecyl-N-tetradecylhydroxylamine; N-hexadecyl-N-heptadecylhydroxylamine; N-hexadecyl-N-octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; and N,N-bis(hydrogenated tallow)hydroxylamine.

[0127] Hydroxylamine may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, or 0.1 wt.% to an upper limit of 0.25 wt.%, 0.5 wt.%, or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0128] Hindered phenols

[0129] Preferred hindered phenols include, but are not limited to, any one or more of the following: (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 1,1,3-tris(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)butane; triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 4,4'-thiobis( 2-tert-butyl-5-methylphenol); 2,2'-thiodiethylidene bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; octadecyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate; tetramethylene(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate)methane; N,N'-hexamethylenebis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionamide]; di(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)thiodipropionate; and octadecyl 3,5-di-(tert-)butyl-4-hydroxyhydrocinnamate.

[0130] Hindered phenols may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, or 0.25 wt.% to an upper limit of 0.3 wt.%, 0.5 wt.%, 0.75 wt.%, or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0131] Organic phosphites and phosphonites

[0132] Preferred organophosphites and phosphonates include, but are not limited to, any one or more of the following: triphenyl phosphite; diphenylalkyl phosphite; phenyl dialkyl phosphite; trilaurate phosphite; tri-octadecyl phosphite; distearate pentaerythritol phosphite; tris(2,4-di-tert-butylphenyl) phosphite; tris(nonylphenyl) phosphite; compounds having formulas (A), (B), (C), (D), (E), (F), (G), (H), (J), (K), and (L):

[0133] (A),

[0134] (B),

[0135]

[0136]

[0137] (L); and 2-butyl-2-ethyl-1,3-propanediol 2,4,6-tri-tert-butylphenol phosphite, bis-(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite, 2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-tert-butylphenol phosphite, and bis-(2,4,6-tri-tert-butyl-phenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite (IRGAFOS®) 168); bis(2,4-dicumylphenyl)pentaerythritol diphosphite (DOVERPHOS® S9228); and tetra(2,4-di-tert-butylphenyl)4,4'-biphenyl-diphosphite (IRGAFOS® P-EPQ).

[0138] Organophosphites or phosphonites may be present in the stabilizer composition of the final polymer article in an amount ranging from a lower limit of 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, or 0.25 wt.% to an upper limit of 0.3 wt.%, 0.5 wt.%, 0.75 wt.%, or 1 wt.%, wherein any lower limit may be used in combination with any suitable upper limit.

[0139] Organic polymer materials

[0140] Suitable for a wide range of stable, non-living organic materials, including but not limited to polyolefins, poly(ethylene-vinyl acetate) (EVA); polyesters, polyethers, polyketides, polyamides, natural and synthetic rubbers, polyurethanes, polystyrene, high-impact polystyrene, polyacrylates, polymethacrylates, polybutyl acrylates, polyacetals, polyacrylonitrile, polybutadiene, polystyrene, acrylonitrile-butadiene-styrene, styrene-acrylonitrile, acrylate-styrene-acrylonitrile, cellulose acetate butyrate, cellulose polymers, polyimides, polyamide-imides, polyether-imides, polyphenylene sulfide, polyphenylene ether polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, polyketides, aliphatic polyketides, thermoplastic olefins (TPO), polyolefin elastomers (POE), amino resin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol / formaldehyde, urea. Formaldehyde and melamine / formaldehyde resins, dried and non-dried alkyd resins, alkyd resins, polyester resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes, epoxy resins, crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic and aromatic glycidyl compounds, which are crosslinked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, amines terminated with activated unsaturated and methylene compounds, ketimides with activated unsaturated and methylene compounds, polyketimides combined with unsaturated acrylic polyacetoacetate resins, polyketimides combined with unsaturated acrylic resins, coating compositions, radiation-curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based paper formulations, photographic film, fibers, waxes, and inks.

[0141] In some embodiments, the inanimate organic material to be stabilized is a polyolefin. Polyolefins suitable for use with the stabilizer compositions according to the embodiments include, but are not limited to:

[0142] (A) Polymers of monoolefins, such as polyethylene, polypropylene, polyisobutylene, polybut-1-ene and poly-4-methylpent-1-ene, polymers of dienes, such as polyisoprene or polybutadiene, and polymers of cycloolefins, such as cyclopentene or norbornene, and polyethylene (which may optionally be crosslinked), such as high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), or ultra-low-density polyethylene (ULDPE).

[0143] (B) Polyolefins, namely polymers of the monoolefins exemplified in (A), preferably polyethylene and polypropylene, can be prepared by various methods, and especially by: i) free radical polymerization (typically under high pressure and at elevated temperatures); or ii) catalytic polymerization using catalysts typically containing one or more metals of Group IVb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alcohols, esters, ethers, amines, alkyl, alkenyl, and / or aryl groups, which can be p- or s-coordinated. These metal complexes can be in free form or immobilized on a substrate, typically on activated magnesium chloride, titanium(III) chloride, alumina, or silica. These catalysts may be soluble or insoluble in the polymerization medium. These catalysts can be used in polymerization themselves, or additional activators can be used, typically metal alkyl groups, metal hydrides, metal alkyl halides, metal alkyl oxides, or metal alkyloxanes, where the metal is an element of Group Ia, IIa, and / or IIIa of the periodic table. The activator can be readily modified with additional ester, ether, amine, or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocene, or single-point catalysts (SSC).

[0144] (C) Mixtures of polymers mentioned in (A), such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), and mixtures of different types of polyethylene (e.g., LDPE / HDPE); and

[0145] (D) Copolymers of monoolefins and dienes with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide, or ethylene / acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes (such as hexadiene, dicyclopentadiene, or ethylene-norbornene); and such copolymers with each other and with the above (A). Mixtures of polymers mentioned herein, such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymers, as well as mixtures thereof with other polymers such as polyamides.

[0146] Particularly preferred organic materials for stabilizing and providing articles include polyolefin polymers, such as i) polymers of monoolefins selected from polyethylene, polypropylene, polyisobutylene, polybut-1-ene, or poly-4-methylpent-1-ene; ii) polymers of dienes selected from polyisoprene or polybutadiene; iii) polymers of cycloolefins selected from cyclopentene or norbornene; iv) polyethylene selected from optionally crosslinked polyethylene, high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), or ultra-low-density polyethylene (ULDPE); v) thermoplastic olefins (TPO); vi) polyolefin elastomers (POE); vii) copolymers thereof; and viiii) mixtures thereof.

[0147] In some embodiments, the stabilizer composition may be present as a stable polymer composition in a stable organic material (e.g., in an article of manufacture) in an amount of 0.005 wt.% to 10.0 wt.% (i.e., any value from 0.01 wt.% to 10.0 wt.% and in between). The stabilizer composition can be in the range of 0.005 wt.%, 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, 0.05 wt.%, 0.075 wt.%, 0.10 wt.%, 0.15 wt.%, 0.20 wt.%, 0.25 wt.%, 0.30 wt.%, 0.35 wt.%, 0.50 wt.%, 0.75 wt.%, 1.0 wt.%, 1.5 wt.% to 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 7.5 wt.%, or 10.0 wt.%. The upper limit of the amount exists, where any lower limit can be used in combination with any suitable upper limit, based on the total weight of the stabilized organic material, and in some cases based on the quantity and type of stabilizing additives added and / or the characteristics of the material to be stabilized.

[0148] Stable polymer composition properties

[0149] Compared to the comparative polymer compositions in which the stabilizer compositions do not contain secondary and tertiary HALS stabilizers and alkoxylated alcohols, the stable polymer compositions according to the embodiments are more resistant to discoloration due to gas fading and thermal oxidation.

[0150] The stable polymer compositions according to the embodiments can exhibit improved heat aging resistance as demonstrated by measurements of yellowness index (YI) and gas fading resistance as demonstrated by measurements of gas fading (e.g., ΔE). ΔYI and ΔE are the differences between samples measured before and after exposure. Yellowness index (YI) and ΔE data were obtained using a Macbeth Color Eye colorimeter according to ASTM D2244-79 with a 1” field of view and a D65 / 10° observer. For the heat aging test, the sample was placed inside a circulating air oven at 80°C, and the yellowness index was measured at different time intervals. For the gas fading resistance test, the sample was placed on a rotating platform within a gas fading instrument developed by Synesqo at 57°C.

[0151] The stable polymer composition according to the embodiments may have a heat aging resistance ΔYI of less than or equal to 3 at 250 h, or less than or equal to 20 at 500 h, or less than or equal to 65 at 850 h, or less than or equal to 75 at 1000 h; and / or a ΔE of less than or equal to 3 at 250 h, or less than or equal to 10 at 500 h, or less than or equal to 30 at 850 h, or less than or equal to 35 at 1000 h.

[0152] The stable polymer composition according to the embodiments may have a gas fading resistance ΔYI of less than or equal to 3.5 at 24 h, or less than or equal to 4.5 at 48 h, or less than or equal to 5 at 72 h; and / or a ΔE of less than or equal to 1.5 at 24 h, or less than or equal to 2.1 at 48 h, or less than or equal to 2.3 at 72 h.

[0153] Methods for manufacturing stable products

[0154] On the other hand, the embodiments herein relate to methods for stabilizing organic materials subjected to degradation and / or discoloration due to the effects of light, oxygen, and / or heat, and the resulting articles. These methods are each implemented by adding a stabilizing amount of a stabilizer composition, as described throughout this specification and the claims, to the organic material to be stabilized, before, during, or after processing. In some embodiments, the stabilizer composition may be added to the organic material to be stabilized as a pure composition. In other embodiments, a masterbatch concentrate, as described herein, may be added to the organic material to be stabilized.

[0155] In some aspects, the embodiments described herein also provide a method for forming stable articles or protecting organic materials from degradation due to light and / or heat from UV irradiation by combining the organic material with a stabilizer composition as described herein. This method may further include forming the organic material into articles by industrial molding, extrusion, molding, blow molding, casting, thermoforming, or compacting the organic material into articles to form stable articles. Additionally, the organic material may be used in the manufacture of industrial fibers or tapes. In some embodiments, the method may include combining the organic material with a masterbatch concentrate as described herein.

[0156] Those skilled in the art will appreciate that these stabilizer compositions and methods are suitable for use with any industrial polymer molding method and are readily adaptable to any industrial polymer molding method, including but not limited to injection molding, rotational molding, blow molding, roll-to-roll molding, metal injection molding, compression molding, transfer molding, dip molding, gas-assisted molding, embedding injection molding, micromolding, reactive injection molding, two-shot injection molding, and any variations or combinations thereof.

[0157] In some embodiments of the method for manufacturing stable articles, the industrial molding method is rotational molding, which includes the following steps:

[0158] a) Fill the mold with a stable polymer composition as defined above.

[0159] b) Rotate the mold about at least one axis while heating the mold in an oven, thereby melting the composition and spreading it onto the walls of the mold;

[0160] c) Cool the mold;

[0161] d) Open the mold; and

[0162] e) Remove the hollow product from the mold. Example

[0163] The following examples are provided to help those skilled in the art further understand certain embodiments of this disclosure. These examples are intended for illustrative purposes and should not be construed as limiting the scope of the various embodiments of this disclosure.

[0164] Table 1. Chemicals Used

[0165]

[0166] Various additive materials were dry-blended with high-density polyethylene (HDPE) from Nova Chemicals according to the formulations in Table 2. The dry-blended granules and additive mixture were processed using a twin-screw extruder (ZSK-30, with an L / D ratio of 24:1) from Werner and Pfleiderer, and the polymer filament was granulated. Next, 3 mm thick square sample sheets were produced using an injection molding machine from Engel.

[0167] As discussed above, yellowness index (YI) data were obtained using a Macbeth Color Eye colorimeter according to ASTM D2244-79 with a 1” field of view and a D65 / 10° observer, and based on L values ​​obtained before and after exposure. a b The color difference (ΔE) is calculated. For thermal aging tests, the sample is placed inside a circulating air oven at 80°C, and the yellowness index is measured at different time intervals. For gas fading resistance tests, the sample is placed on a rotating platform within a gas fading instrument developed by Strasbourg at 57°C. For weathering resistance tests, the sample is placed in a Q-Lab QUV-B313 accelerated weathering tester. ΔYI is the difference in yellowness index between the sample measured before and after exposure. Lower ΔE and ΔYI indicate smaller color difference and lower yellowness increase after exposure.

[0168] Table 2. HDPE formulations with stabilizers

[0169]

[0170] Table 3. Heat aging resistance of HDPE stabilized with HALS, UV-1164, L-55 and antioxidants.

[0171]

[0172] The results obtained from Table 3 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the change in yellowness index is further reduced after exposure to air oxidative aging at 80°C.

[0173] Table 4. Heat aging resistance of HDPE stabilized with HALS, UV-1164, L-55 and antioxidants

[0174]

[0175] The results obtained from Table 4 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the color difference (ΔE) is further reduced after exposure to air oxidative aging at 80°C.

[0176] Table 5. Heat aging resistance of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants

[0177]

[0178] The results obtained from Table 5 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the change in yellowness index is further reduced after exposure to air oxidative aging at 80°C.

[0179] Table 6. Heat aging resistance of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants

[0180]

[0181] The results obtained from Table 6 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the color difference (ΔE) is further reduced after exposure to air oxidative aging at 80°C.

[0182] Table 7. Resistance to gas fading of HDPE stabilized with HALS, UV-1164, L-55 and antioxidants

[0183]

[0184] The results obtained from Table 7 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the change in yellowness index is further reduced after gas fading at 57°C.

[0185] Table 8. Resistance to gas fading of HDPE stabilized with HALS, UV-1164, L-55 and antioxidants

[0186]

[0187] The results obtained from Table 8 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the color difference (ΔE) is further reduced after gas fading at 57°C.

[0188] Table 9. Resistance to gas fading of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants

[0189]

[0190] The results obtained from Table 9 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the change in yellowness index is further reduced after gas fading at 57°C.

[0191] Table 10. Resistance to gas fading of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants

[0192]

[0193] The results obtained from Table 10 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the color difference (ΔE) is further reduced after gas fading upon exposure to 57°C.

[0194] Table 11. Weather resistance test of QUV-B 313 HDPE stabilized with HALS, UV-1164, L-55 and antioxidants

[0195]

[0196] The results obtained from Table 11 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the yellowness index changes decrease or remain similar after exposure to QUV-B 313.

[0197] Table 12. Weather resistance test of HDPE stabilized with HALS, UV-1164, L-55 and antioxidants for QUV-B 313

[0198]

[0199] The results obtained from Table 12 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, and antioxidants, the color difference (ΔE) is reduced or remains similar after exposure to QUV-B 313.

[0200] Table 13. Weather resistance test of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants for QUV-B 313

[0201]

[0202] The results obtained from Table 13 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the yellowness index changes after exposure to QUV-B 313 decrease or remain similar.

[0203] Table 14. Weather resistance test of HDPE stabilized with HALS, UV-1164, UV-2908, L-55 and antioxidants for QUV-B 313

[0204]

[0205] The results obtained from Table 14 demonstrate that when L-55 and tertiary HALS are added to a stabilizer system containing secondary HALS, triazine UV absorbers, hindered benzoates, and antioxidants, the color difference (ΔE) is reduced or remains similar after exposure to QUV-B 313.

[0206] An example of rotational molding simulation:

[0207] Linear medium-density polyethylene resin (NOVAPOL® TF-0338-E) and additives were dry-blended according to the formulation in Table 15 and extruded at a melt temperature of 370°F using a single-screw extruder (model DS-15-HM) from Davis-Standard Corp. The extruded polymer filament was then granulated. The extruded granules were then ground using a mill from PowerKing and sieved through a set of sieves with different porosities. The ground polymer with particle sizes ranging from 150 microns to 425 microns was collected for further evaluation.

[0208] To simulate rotary molding, 20 grams of powdered polymer with a particle size of 150 to 425 micrometers were placed on an aluminum plate. A square hollow metal mold (melt pool) with a height of 25 mm was then placed above the polymer powder. The powder was compacted using a press at room temperature. The aluminum plate containing the compacted polymer powder and the melt pool was then transferred to the top of the lower platen of a compression mold set at 450°F. The lower platen of the compression mold was then raised to near the upper platen, also set at 450°F. The gap between the lower and upper plates of the compression mold was set to 35 mm. The apparatus was designed such that the surface of the polymer powder did not directly contact the heated upper platen of the compression mold. As the polymer powder melted, it fused together without any external shear to produce a uniform article simulating rotary molding. After heating for 10 minutes, the aluminum plate containing the melt pool containing the molten polymer was removed from the heated platen and cooled to room temperature using a cooling fan, and the melt pool was then removed. The resulting polymer article has a thickness between 5.3 mm and 5.5 mm. When the polymer article is cooled to room temperature, the color difference is obtained using a Color Eye colorimeter according to ASTM D2244-79.

[0209] Table 16 lists the yellowness index values ​​of the products produced after simulating rotary molding. The mold side refers to the side where the polymer is in direct contact with the hot platen of the compression mold, and the air side refers to the side where the polymer is in contact with the hot air generated by the heated upper platen of the compression mold. It was found that the addition of L-55 reduced the color difference of the products. When a combination of secondary and tertiary HALS was used in formulations containing L-55, the color difference was further reduced.

[0210] Table 15. Formulations used for rotational molding simulation

[0211]

[0212] Table 16. Yellowness Index of Products Produced After Rotational Molding Simulation

[0213]

[0214] While only a few exemplary embodiments have been described in detail above, those skilled in the art will readily understand that many modifications can be made to the exemplary embodiments without substantially departing from the invention. Therefore, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, the device plus function clause is intended to cover not only structural equivalents but also equivalent structures as described herein.

Claims

1. A stable polymer composition comprising: a. Organic polymer materials to be stabilized and b. A stabilizer composition comprising: i. At least one UV absorber selected from the o-hydroxyphenyl-triazine UV absorber category; ii. Secondary hindered amine light stabilizers (sec.-HALS); iii. At least one antioxidant selected from hindered phenols, phosphites, phosphonites, or any mixture thereof; iv. Tertiary hindered amine light stabilizers (tert.-HALS); v. Alkoxylated alcohols; and vi. Optionally hindered benzoate; in, Compared to polymer compositions in which the stabilizer composition does not contain tertiary HALS stabilizers and alkoxylated alcohols, this stabilized polymer composition is more resistant to discoloration caused by gas fading and thermal oxidation.

2. The stable polymer composition according to claim 1, wherein, The ratio of sec.-HALS to tert.-HALS is between 10:1 and 1:

10.

3. The stable polymer composition according to claim 1 or 2, wherein, The ratio of sec.-HALS to tert.-HALS is between 5:1 and 1:

5.

4. The stable polymer composition according to any one of claims 1 to 3, wherein, The ratio of tert.-HALS to alkoxylated alcohols is between 100:1 and 1:

1.

5. The stable polymer composition according to any one of claims 1 to 4, wherein, The ratio of tert.-HALS to alkoxylated alcohol is between 50:1 and 2:1, and preferably between 20:1 and 4:

1.

6. The stable polymer composition according to any one of claims 1 to 5, wherein, The stabilizer composition is present in an amount of 0.005 to 10 wt.%, preferably 0.01 to 5 wt.%, and more preferably 0.1 to 2 wt.%, based on the total weight of the polymer.

7. The stable polymer composition according to any one of claims 1 to 6, wherein, The stabilizer composition comprises at least one o-hydroxyphenyl-triazine UV absorber according to formula (I). (I)， Each R 34 and R 35 Independently, it is C6-C 10 Aryl, mono- or di-C1-C 12 Hydroxyl-substituted amino groups, C2-C 12 Alkyl group, C1-C 12 Alkyl, C1-C 10 Acyl or C1-C 10 Alkoxy Among them, C6-C 10 The aryl group can be optionally replaced by OH, halogen, or C1-C at 1 to 3 substituted positions. 12 Alkyl, C1-C 12 Alkoxy, C1- 12 Alkoxy esters, C2- 12 At least one of alkylyl or phenyl groups is substituted, wherein the phenyl group is optionally substituted at one to three positions with OH, halogen, C1- 12 Alkyl, C1- 12 Alkoxy, C1- 12 alkoxy esters, or C2- 12 At least one substitution of the alkyl acyl group; and Each R 36 Independently, it is OH, halogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C1-C 12 Alkoxy esters, C2-C 12 Alkyl, phenyl, or C1-C 12 Acyl group.

8. The stable polymer composition according to claim 7, wherein, o-Hydroxyphenyl-triazine UV absorbers are at least one of the following: 4,6-Diphenyl-2-(4-hexyloxy-2-hydroxyphenyl)-triazine, 4,6-Bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-octyloxyphenyl)-triazine, 4,6-Bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-isooctyloxyphenyl)-triazine, 2,4-Bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-triazine, A mixture of 4,6-bis(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-dodecyloxy-2-hydroxypropoxy)phenyl)-triazine and 4,6-bis-(2,4-dimethylphenyl)-2-(2-hydroxy-4-(3-tetratekoxy-2-hydroxypropoxy)phenyl)-triazine. 4,6-Bis(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-triazine, 4,6-Bis(2,4-dimethylphenyl)-2-(2-hydroxy-4(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-phenyl)-triazine, 2,4-Bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-[(octoxycarbonyl)ethoxy]phenyl]-triazine, 2,4-Bis(4-biphenyl)-6-[2-hydroxy-4-[(octoxycarbonyl)ethoxy]phenyl]-triazine, 2,4-Bis(4-biphenyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-triazine, 2,4-Bis(2-hydroxy-4-butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-triazine, 2,4,6-Tris[2-hydroxy-4-(3-sec-butoxy-2-hydroxypropoxy)-phenyl]-triazine, or 2,4,6-Tris[2-hydroxy-4-[(octoxycarbonyl)ethyleneoxy]phenyl]-triazine.

9. The stable polymer composition according to any one of claims 1 to 8, wherein, The stabilizer composition further comprises at least one of a plurality of UV absorbers (UVA) selected from the group consisting of: 2-hydroxybenzophenone compounds; o-hydroxyphenylbenzotriazole compounds; oxaloyl aniline; cyanoacrylate; benzoxazinone compounds; and mixtures thereof.

10. The stable polymer composition according to claim 9, wherein, The 2-hydroxybenzophenone is at least one of the following: 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2'-dihydroxy-4,4'-di-methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-diethoxybenzophenone, 2,2'-dihydroxy-4,4'-dipropoxybenzophenone, 2,2'-dihydroxy-4,4'-dibutoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-ethoxybenzophenone 2,2'-Dihydroxy-4-methoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2,2'-dihydroxy-4-ethoxy-4'-propoxybenzophenone, 2,2'-dihydroxy-4-ethoxy-4'-butoxybenzophenone, 2,3'-dihydroxy-4,4'-dimethoxybenzophenone, 2,3'-dihydroxy-4-methoxy-4'-butoxybenzophenone, 2-hydroxy-4,4',5'-trimethoxybenzophenone, 2-hydroxy-4,4',6'-tributoxybenzophenone, 2-hydroxy-4-butoxy-4',5'-dimethoxybenzophenone, 2-hydroxy-4-ethoxy-2',4'- Dibutylbenzophenone, 2-hydroxy-4-propoxy-4',6'-dichlorobenzophenone, 2-hydroxy-4-propoxy-4',6'-dibromobenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-ethoxybenzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxy-4'-ethylbenzophenone, 2-hydroxy-4-methoxy-4'-propylbenzophenone, 2-hydroxy-4-methoxy-4'-butylbenzophenone, 2-hydroxy-4-methoxy-4'-tert-butylbenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2- Hydroxy-4-methoxy-2'-chlorobenzophenone, 2-hydroxy-4-methoxy-4'-bromobenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4,4'-dimethoxy-3-methylbenzophenone, 2-hydroxy-4,4'-dimethoxy-2'-ethylbenzophenone, 2-hydroxy-4,4',5'-trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-methylbenzophenone, 2-hydroxy-4-ethoxy-4'-ethylbenzophenone, 2-hydroxy-4-ethoxy-4'-propylbenzophenone, 2-hydroxy-4-ethoxy-4'-butylbenzophenone, 2-hydroxy-4-ethoxy-4'-methoxybenzophenone, 2-hydroxy-4,4'-Diethoxybenzophenone, 2-hydroxy-4-ethoxy-4'-propoxybenzophenone, 2-hydroxy-4-ethoxy-4'-butoxybenzophenone, 2-hydroxy-4-ethoxy-4'-chlorobenzophenone, or 2-hydroxy-4-ethoxy-4'-bromobenzophenone.

11. The stable polymer composition according to claim 9, wherein, The 2-(2'-hydroxyphenyl)benzotriazole is at least one of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-methyl-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-cyclohexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dimethylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)-5-chloro-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-... 2-(3',5'-di-tert-pentyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octoxycarbonylethyl)phenyl)benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)6-benzotriazole-2-ylphenol], 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole transesterification product with polyethylene glycol 300 (TINUVIN™) 1130), 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-(2-hydroxyethyl)phenyl)benzotriazole, 2-(2'-hydroxy-5'-(2-methacryloyloxyethyl)phenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5 2-Chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-5'-methyl-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-5'-(2-octoxycarbonylethyl)-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(5'-methyl-2'-hydroxyphenyl)benzotriazole or 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole.

12. The stable polymer composition according to claim 9, wherein, The benzoxazinone is at least one of the following: 2-methyl-3,1-benzoxazin-4-one, 2-butyl-3,1-benzoxazin-4-one, 2-phenyl-3,1-benzoxazin-4-one, 2-(1-or 2-naphthyl)-3,1-benzoxazin-4-one, 2-(4-biphenyl)-3,1-benzoxazin-4-one, 2-p-nitrophenyl-3,1-benzoxazin-4-one, 2-m-nitrophenyl-3,1-benzoxazin-4-one, 2-p-benzoylphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-p-methoxyphenyl-3,1-benzoxazin-4-one, 2-o-methoxyphenyl-3,1-benzoxazin-4-one, 2-cyclohexyl-3,1-benzoxazin-4-one, Ketones, 2-p-(or m-)phthalimide, phenyl-3,1-benzoxazin-4-one, N-phenyl-4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N-benzoyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, N-benzoyl-N-methyl-4-(3,1-benzoxazin-4-one-2-yl)aniline, 2-[p-(N-phenylcarbamoyl)phenyl]-3,1-benzoxazin-4-one, 2-[p-(N-phenyl-N-methylcarbamoyl)phenyl]-3,1-benzoxazin-4-one, 2,2'-bis(3,1-benzoxazin-4-one), 2,2'-ethylidene bis(3,1-benzoxazin-4-one), 2 2,2'-Tetramethylenebis(3,1-benzoxazin-4-one), 2,2'-Hexamethylenebis(3,1-benzoxazin-4-one), 2,2'-Dedecylethylenebis(3,1-benzoxazin-4-one), 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2,6- or 1,5-naphthalene)bis(3,1-benzoxazin-4-one), 2,2'-(2-methyl-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(2-nitro-p-phenylene)bis(3,1-benzoxazin-4-one) 2,2'-(2-chloro-p-phenylene)bis(3,1-benzoxazin-4-one), 2,2'-(1,4-cyclohexylene)bis(3,1-benzoxazin-4-one), N-p-(3,1-benzoxazin-4-one-2-yl)phenyl, 4-(3,1-benzoxazin-4-one-2-yl)phthalimide, N-p-(3,1-benzoxazin-4-one-2-yl)benzoyl, 4-(3,1-benzoxazin-4-one-2-yl)aniline, 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)benzene, 1,3,5-tris(3,1-benzoxazin-4-one-2-yl)naphthalene, or 2,4,6-tris(3,1-benzoxazin-4-one-2-yl)naphthalene.

13. The stable polymer composition according to any one of claims 1 to 12, wherein, This hindered amine light stabilizer (tert.-HALS) is selected from at least one of the following: bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis(1,2,2,6,6-pentamethyl-4-piperidinyl); bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl-4-hydroxybenzyl malonate; a condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; a mixture of bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate and methyl 1,2,2,6,6-pentamethylpiperidin-4-yl sebacate (TINUVIN™). 292); bis(1,2,2,6,6-pentamethylpiperidin-4-yl)n-butyl 3,5-di-tert-butyl-4-hydroxybenzyl malonate; condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; 1,2,2,6,6-pentamethylpiperidin-4-yl stearate; 1,2,2,6,6-pentamethylpiperidin-4-yl dodecanoate; methylated condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis-(3 A condensate of (-aminopropylamino)ethane; tetra(1,2,2,6,6-pentamethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; a mixture of 4-hexadecyloxy- and 4-stearoyloxy-1,2,2,6,6-pentamethylpiperidin; 1,5,8,12-tetra[4,6-bis(N-butyl-N-1,2,2,6,6-pentamethyl-4-piperidinylamino)-1,3,5-triazin-2-yl]-1,5,8,12-tetraazadodecane; a reaction product of a polymer of 1,2,3,4-butanetetracarboxylic acid with β,β,β′-tetramethyl-2,4,8,10-tetraoxyspiro[5,5]undecane-3,9-diethanol and 1,2,2,6,6-pentamethyl-4-piperidinyl ester.

14. The stable polymer composition according to any one of claims 1 to 13, wherein, The secondary hindered amine light stabilizer (sec.-HALS) is selected from: Bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate; C 12 -C 21 Saturated fatty acids and C 18 A mixture of 2,2,6,6-tetramethylpiperidin-4-yl esters of unsaturated fatty acids; bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; 2,2,6,6-Tetramethylpiperidin-4-yl stearate; 2,2,6,6-Tetramethylpiperidin-4-yl ester of dodecanoic acid; A condensation of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; Tris(2,2,6,6-tetramethylpiperidin-4-yl) ester of azidotriacetate; 4-Stearoxy-2,2,6,6-Tetramethylpiperidine; A condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine; Condensates of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, di-n-butylamine and 2,4,6-trichloro-1,3,5-triazine; A condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; A condensate of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; A condensate of N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; Tetra(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate; 1,2,3,4-Butanetetracarboxylic acid 2,2,6,6-tetramethylpiperidin-4-yltridecyl ester; or N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethylpiperidin-4-yl)formamide.

15. The stable polymer composition according to any one of claims 1 to 14, wherein, The hindered benzoate compound is based on formula (VII): (VII), in R 21 and R 22 Each of them is independently selected from C1-C 12 alkyl; T is O, where R 24 Is it H or C1-C? 30 hydrocarbon group; and R 23 Is it H or C1-C? 30 Hydrocarbon group.

16. The stable polymer composition according to claim 15, wherein, The hindered benzoate compound is selected from the group consisting of: 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; octyl-3,5-di-tert-butyl-4-hydroxybenzoate; decyl-3,5-di-tert-butyl-4-hydroxybenzoate; dodecyl-3 ,5-di-tert-butyl-4-hydroxybenzoate; tetradecyl-3,5-di-tert-butyl-4-hydroxybenzoate; benzyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; butyl-3-[3-tert-butyl-4-(3,5-di-tert-butyl-4-hydroxybenzoyloxy)phenyl]propionate; and mixtures thereof.

17. The stable polymer composition according to any one of claims 1 to 16, wherein, The stabilizer composition comprises a hindered phenolic antioxidant selected from the following: (1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione; 1,1,3-tris(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)butane; triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; 4,4'-thiobis( 2-tert-butyl-5-methylphenol); 2,2'-thiodiethylidene bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; octadecyl 3-(3'-tert-butyl-4'-hydroxy-5'-methylphenyl)propionate; tetramethylene(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate)methane; N,N'-hexamethylenebis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionamide]; di(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)thiodipropionate; and octadecyl 3,5-di-(tert-)butyl-4-hydroxyhydrocinnamate.

18. The stable polymer composition according to any one of claims 1 to 18, further comprising an organophosphite or phosphonite.

19. The stable polymer composition according to claim 18, wherein, The organophosphite or phosphonite is selected from: triphenyl phosphite; diphenylalkyl phosphite; diphenyl phosphite; trilaurate phosphite; tri-octadecyl phosphite; distearate pentaerythritol phosphite; tris(2,4-di-tert-butylphenyl) phosphite; tris(nonylphenyl) phosphite; and compounds having formulas (A), (B), (C), (D), (E), (F), (G), (H), (J), (K), and (L). (A)， (B)， (C)， (D)， (E)， (F)， (G)， (H)， (J)， (K)， (L); and 2-Butyl-2-ethyl-1,3-propanediol 2,4,6-tri-tert-butylphenol phosphite, bis-(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-butyl-2-ethyl-1,3-propanediol 2,4-di-cumylphenol phosphite, 2-butyl-2-ethyl-1,3-propanediol 4-methyl-2,6-di-tert-butylphenol phosphite, and bis-(2,4,6-tri-tert-butyl-phenyl) pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite; (bis-(2,4-dicumylphenyl) pentaerythritol diphosphite; and tetra(2,4-di-tert-butylphenyl) 4,4'-biphenyl-diphosphite.

20. The stable polymer composition according to any one of claims 1 to 19, wherein, The stabilizer composition contains an inorganic UV blocker.

21. The stable polymer composition according to any one of claims 1 to 20, wherein, The inorganic UV blocker is selected from titanium oxide, zinc oxide, cerium oxide, and barium sulfate.

22. The stable composition according to any one of claims 1 to 21, wherein, The alkoxylated alcohol is based on formula (III): R–(YOUR SIDE2) y –OH(III), Where R is a hydrocarbon group having 12 to 60 carbon atoms; R' is selected from H or C1-C4 alkyl; R” is a hydrocarbon group having 1 to 10 carbon atoms; and y is an integer from 1 to 100.

23. The stable composition according to claim 22, wherein, In equation (III), R is C 12 -C 30 Alkyl group and R' is H.

24. The stabilizer composition according to claim 22 or 23, wherein, y is 1 to 75.

25. The stable polymer composition according to any one of claims 1 to 24, further comprising a stable amount of a co-additive selected from the group consisting of: nucleating agents, fillers, metal stearates, reinforcing agents, plasticizers, lubricants, rheology modifiers, catalysts, leveling agents, optical brighteners, antistatic agents, foaming agents, flame retardants, dyes, pigments, thioesters, hydroxylamine, benzofuranone, nitrone, and mixtures thereof.

26. The stable polymer composition according to any one of claims 1 to 25, wherein, The polymeric organic material to be stabilized is selected from the group consisting of: polyolefins, poly(ethylene-vinyl acetate) (EVA), polyesters, polyethers, polyketides, polyamides, natural and synthetic rubbers, polyurethanes, polystyrene, high-impact polystyrene, polyacrylates, polymethacrylates, polybutyl acrylates, polyacetals, polyacrylonitrile, polybutadiene, polystyrene, acrylonitrile-butadiene-styrene, styrene-acrylonitrile, acrylate styrene-acrylonitrile, cellulose acetate butyrate, cellulose polymers, polyimides, polyamide-imides, polyether-imides, polyphenylene sulfide, polyphenylene ether polysulfone, polyethersulfone, polyvinyl chloride, polycarbonate, polyketides, aliphatic polyketides, thermoplastic olefins (TPO), polyolefin elastomers (POE), amino resin crosslinked polyacrylates and polyesters, polyisocyanate crosslinked polyesters and polyacrylates, phenol / formaldehyde, urea. Formaldehyde and melamine / formaldehyde resins, dried and non-dried alkyd resins, alkyd resins, polyester resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes, epoxy resins, crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic and aromatic glycidyl compounds, which are crosslinked with anhydrides or amines, polysiloxanes, Michael addition polymers, amines, amines terminated with activated unsaturated and methylene compounds, ketimides with activated unsaturated and methylene compounds, polyketimides combined with unsaturated acrylic polyacetoacetate resins, polyketimides combined with unsaturated acrylic resins, coating compositions, radiation-curable compositions, epoxy melamine resins, organic dyes, cosmetics, cellulose-based paper formulations, photographic film, fibers, waxes, and inks.

27. The stable polymer composition according to claim 26, wherein, The polymeric organic material to be stabilized is a polyolefin selected from the group consisting of: i) polymers of monoolefins selected from polyethylene, polypropylene, polyisobutylene, polybut-1-ene, or poly-4-methylpent-1-ene; ii) polymers of dienes selected from polyisoprene or polybutadiene; iii) polymers of cyclopentene or norbornene; iv) polyethylene selected from optionally crosslinked polyethylene, high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), or ultra-low-density polyethylene (ULDPE); v) thermoplastic olefins (TPO); vi) polyolefin elastomers (POE); vii) copolymers thereof; and viiii) mixtures thereof.

28. A method for manufacturing a stable article, the method comprising adding a stable polymer composition according to any one of claims 1 to 27 to an apparatus or method for carrying out: industrial molding; industrial fiber manufacturing; industrial tape manufacturing; and extruding sheets.

29. The method according to claim 28, wherein, The apparatus or method for industrial molding is selected from injection molding, rotational molding, blow molding, roll-to-roll molding, metal injection molding, compression molding, transfer molding, dip molding, gas-assisted molding, embedding injection molding, micro molding, reaction injection molding, and dual-emission injection molding.

30. The method according to claim 28 or 29, wherein, The method for industrial molding is rotational molding, which includes the following steps: a) Fill the mold with the stable polymer composition. b) Rotate the mold about at least one axis while heating the mold in an oven, thereby melting the composition and spreading it onto the wall of the mold; c) Cool the mold; d) Open the mold; and e) Remove the hollow product from the mold.

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